Insecticidal, acaricidal and molluscicidal 1-(substituted)thioalkylpyrroles

ABSTRACT

There are provided 1-(substituted)thioalkylpyrrole compounds of formula I  (* CHEMICAL STRUCTURE *) I the use thereof for the control of insect, acarid and mollusk pests and methods and compositions for the protection of crops from the ravages of said pests.

This application is a division of copending application Ser. No.07/804,260, filed Dec. 4, 1991, now U.S. Pat. No. 5,254,559.

BACKGROUND OF THE INVENTION

Pyrrole compounds useful as insecticides, acaricides and molluscicidesare described in U.S. Pat. No. 5,010,098 and copending applications Ser.No. 430,601 filed on Nov. 6, 1989, Ser. No. 447,726 filed on Dec. 8,1989, Ser. No. 522,299 filed on May 11, 1990, Ser. No. 600,054 filed onOct. 18, 1990 and U.S. Pat. No. 5,204,332. However, none of thesereferences disclose pyrrole compounds having a (substituted)thioalkylmoiety on the pyrrole ring nitrogen atom. Patent applications Ser. Nos.803,289 and 803,294 filed concurrently herewith describe certaintrifluoromethylsulfonylpyrroles useful as insecticidal and fungicidalagents, respectively. However, the pyrrole compounds of the presentinvention are not described therein. Copending patent application Ser.No. 803,295, filed concurrently herewith describes the fungicidal use of1-(substituted)thioalkylpyrrole compounds.

SUMMARY OF THE INVENTION

The present invention provides 1-(substituted)thioalkylpyrrole compoundsof formula I ##STR2## wherein W is CN or NO₂ ;

X is halogen or phenyl optionally substituted with one to three C₁ -C₃alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃alkylsulfonyl, halogen, CN, NO₂, CF₃, R₄ CF₂ B, R₅ CO or NR₆ R₇ groups;

Y is CF₃, halogen or phenyl optionally substituted with one to three C₁-C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃alkylsulfonyl, halogen, CN, NO₂, CF₃, R₄ CF₂ B, R₅ CO or NR₆ R₇ groups;

Z is halogen or CF₃ ;

R₁ is hydrogen, C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl;

R₂ and R₃ are each independently hydrogen, C₁ -C₆ alkyl or C₃ -C₆cycloalkyl;

R₄ is hydrogen, fluorine, CHF₂, CHFCl or CF₃ ;

R₅ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₆ R₇ ;

R₆ is hydrogen or C₁ -C₃ alkyl;

R₇ is hydrogen, C₁ -C₃ alkyl or R₈ CO;

R₈ is hydrogen or C₁ -C₃ alkyl;

B is S(O)_(q) or O;

m, n, p and q are each independently an integer of 0, 1 or 2 with theproviso that the sum (P+M) must be greater than 0; ##STR3## CN, C₁ -C₆alkyl optionally substituted with one or more phenyl, CN or halogengroups or phenyl optionally substituted with one to three C₁ -C₃ alkyl,C₁ -C₃ alkoxy, halogen, CN, NO₂, CF₃ or NR₂₀ R₂₁ groups;

A is O or S;

R₉ is C₁ -C₆ alkyl or phenyl;

R₁₀ is C₁ -C₆ alkyl;

R₁₁ and R₁₂ are each independently hydrogen, C₁ -C₆ alkyl or may betaken together with the atom to which they are attached to form a 5- to7-membered ring;

R₁₃ is C₁ -C₄ alkyl;

R₁₄ is hydrogen, C₁ -C₄ alkyl or may be taken together with either R₁₅or R₁₇ and the atoms to which they are attached to form a 5- to7-membered ring optionally substituted with one or two C₁ -C₃ alkylgroups;

R₁₅ and R₁₆ are each independently hydrogen or C₁ -C₄ alkyl;

R₁₇ is C₁ -C₄ alkyl or when taken together with R₁₄ and the atoms towhich they are attached may form a 5- to 7-membered ring optionallysubstituted with one or two C₁ -C₃ alkyl groups;

R₁₈ and R₁₉ are each independently hydrogen or C₁ -C₃ alkyl or whentaken together may form a ring wherein R₁₈ R₁₉ is represented by--CH═CH--CH═CH--;

R₂₀ and R₂₁ are each independently hydrogen or C₁ -C₃ alkyl and

the acid addition salts therof.

There are also provided compositions and methods for the control ofinsect, acarid and mollusk pests. And, further, a method is provided forthe protection of crops, both growing and harvested, from infestationand attack by, said pests.

DETAILED DESCRIPTION OF THE INVENTION

Throughout time, agriculturalists have been seeking effective andefficient means of combatting insect, acarid and mollusk pests. Saidpests cause considerable economic damage to essential crops when leftunchecked. There is a real need in the art for alternative, effectivecompounds and compositions useful for agricultural applications asinsecticidal, acaricidal and molluscicidal agents.

It is an object of the present invention to provide1-(substituted)thioalkylpyrrole compounds that are effective agents forthe control of insect, acarid, and mollusk pests. It is a further objectof this invention to provide methods and compositions for the protectionof agronomic crops, both growing and harvested, from the ravages of saidpests.

The 1-(substituted)thioalkylpyrrole compounds of the invention have thestructural formula I ##STR4## wherein W, X, Y, Z, R₁, R₂, R₃, m, n, pand Q are as described hereinabove. The term halogen, as used in thespecification and claims, designates chlorine, fluorine, bromine andiodine. Acid addition salts are those known in the art such as hydrogenhalides, hydrogen sulfates, sulfates, sulfonates and the like.

Preferred compounds of the invention are those having structure II##STR5## wherein W is CN, n is O and X, Y, Z, R₁, R₂, R₃, m, p and Q areas described hereinabove.

Among the formula II compounds of the present invention which areespecially useful for the control of terrestial gastropods such assnails and slugs and aquatic or semi-aquatic mollusks such as cowriesand limpets are those wherein W is CN, X, Y and Z are independentlyhalogen or CF₃, n and m are O, p is 1, and Q is as describedhereinabove.

Compounds of formula II which are particularly effective insecticidaland acaricidal agents are those wherein W is CN or NO₂ ; X is phenyloptionally substituted with one to three C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁-C₃ alkylthio, halogen or CF₃ groups; Y and Z are independently halogenor CF₃ ; n and m are O, p is 1, and Q is as described hereinabove.

Certain 1-(substituted)thioalkylpyrrole compounds of formula I may beprepared by reacting a pyrrole compound of formula III with a suitabledithiocarbamate, thiocarbamate, thiophosphate or mercaptate alkali metalsalt. A specific example of this reaction is illustrated in flow diagramI. ##STR6##

Moreover, certain compounds of formula I may be prepared by reacting theappropriate halomethyl thioether with a pyrrole compound of formula IVin the presence of a base. A representative example is shown in flowdiagram II ##STR7##

Compounds of formulas III and IV are described in U.S. Pat. No.5,010,098 and copending patent applications Ser. No. 634,288 filed onDec. 16, 1990 and U.S. Pat. No. 5,204,332 and incorporated herein byreference thereto.

Other compounds of formula I may be prepared by reacting a1-(halomethyl)pyrrole compound of formula III with a suitable thioureareagent. In this reaction scheme, the product may be isolated as itsacid addition salt. The free base may be obtained using standardprocedures such as treatment with excess aqueous base and filtration orextraction of the desired product with a suitable solvent. Anillustrative example is shown in flow diagram III. ##STR8##

Further compounds of formula I may be prepared by reacting a pyrrolecompound of formula IV with a halomethyl compound of formula V whereinR₁ is defined hereinabove in the presence of a base such as an alkalimetal alkoxide to form the pyrrole intermediate of formula VI. Theformula VI intermediate may then be halogenated using conventionalhalogenating reagents such as N-bromosuccinimide (NBS) to give thedesired 1-(haloalkyl)pyrrole second intermediate of formula VII whichmay then be reacted with an alkali metal thiocarbamate, dithiocarbamate,mercaptate, thiophosphate or the like to yield the1-(substituted)thioalkylpyrrole product as shown in flow diagram IV.##STR9##

Yet further pyrrole compounds of the invention may be prepared byreacting the formula IV pyrrole with an epoxide of formula VIII in thepresence of a base to give the β-hydroxy pyrrole intermediate of formulaIX which can then be converted to the corresponding tosylate of formulaX by reaction with p-toluenesulfonyl chloride (tsCl) in the presence ofan organic base such as pyridine. The tosylate intermediate of formula Xmay then be reacted with an alkali metal thiocarbamate, dithiocarbamate,mercaptate, thiophosphate or the like to yield the desired1-(substituted)thioalkylpyrrole product as shown in flow diagram V.##STR10##

Specific examples are provided below for the purpose of illustration.The examples utilize the above reaction schemes and also provide furthermeans for preparing even more compounds of the invention which are notspecifically described hereinabove.

The 1-(substituted)thioalkylpyrrole compounds of the present inventionare effective for controlling insect, acarid and mollusk pests. Saidpyrroles are also effective for protecting growing or harvested cropsfrom said pests.

In practice, generally about 10 ppm to 10,000 ppm, preferably about 100to 5,000 ppm, of the formula I compound dispersed in a liquid carrier,when applied to the plants or the soil or water in which the plants aregrowing, is effective to protect the plants from attack by insects oracarids or mollusks. Compositions of the invention are also effectivefor protecting turf grass from attack by pests such as grubs, chinchbugs and the like. Applications, such as spray applications, ofcompositions of the invention are generally effective at rates whichprovide about 0.125 kg/ha to 4.0 kg/ha of the active1-(substituted)thioalkylpyrrole compound. Of course, higher rates ofapplication of said pyrrole compounds may be used, if desired.

Advantageously, the compounds of the invention may be used effectivelyin conjunction with, or in combination with, other biological chemicals,including other insecticides, nematicides, acaricides and mulluscicidessuch as phosphates, carbamates, pyrethroids, halobenzoylureas,arylpyrroles, nitropyrroles, pyrrole carbonitriles and the like.

A particularly effective method for the control of terrestrialgastropods is to proffer the compound of formula I in a baitformulation. The bait formulation can be widely varied, but in generalmay contain about 3% to 20% wt/wt, preferably about 5% to 10% wt/wt, ofthe active ingredient, about 40% to 50% wt/wt of a solid ediblesubstance, about 5% to 10% wt/wt of a carbohydrate source and, theremainder of the formulation, about 30% to 50% of a consumable liquidsuch as water. The carbohydrate source may be selected from sugar,molasses, corn syrup and the like.

In addition to the above-said bait formulations and spray formulations,the 1-(substituted)thioalkylpyrrole compounds of the present inventionmay be formulated into granular compositions, flowable compositions,wettable powders, dusts, microemulsions, emulsifiable concentrates andthe like. All compositions which lend themselves to soil, water andfoliage application and provide effective plant protection are suitable.Compositions of the invention include the formula I compound admixedwith an inert solid or liquid carrier.

Where compositions of the invention are to be employed in combinationtreatments with other pesticidal agents, the composition may be appliedas an admixture of the components or may be applied sequentially.

For a more clear understanding of the invention, specific detailedexamples of it are set forth below. These examples are merelyillustrative, and are not to be understood as limiting the scope andunderlying principles of the invention in any way. Unless otherwisenoted, all parts are parts by weight. H¹ NMR and C¹³ NMR designateproton nuclear magnetic resonance and carbon 13 nuclear magneticresonance, respectively.

EXAMPLE 1 Preparation of4-bromo-2-(p-chlorophenyl)-1-[(imidazol-2-ylthio)methyl]-5-trifluoromethylpyrrole-3-cartonitrilehydrobromide ##STR11##

A mixture of4-bromo-1-(bromomethyl)-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile(0.88 g, 0.002 mol) and 4-imidazoline-2-thione (0.23 g, 0.002 mol) inisopropanol is heated at reflux temperature for 3 hours, cooled to roomtemperature and filtered. The filtercake is washed with isopropanol andair-dried to give the title product as a white solid, 0.81 g (75%yield), mp 221°-223° C(dec).

EXAMPLES2-20 Preparation of 1-[(substituted)thiomethyl]pyrroles

Using the procedure described in Example 1 and employing theappropriately substituted 1-(halomethyl)pyrrole substrate and a suitablethiourea reagent, the following 1-[(substituted)thiomethyl]pyrrolecompounds shown in Table I are obtained.

                                      TABLE I                                     __________________________________________________________________________     ##STR12##                                                                    Ex.                            acid                                           No.                                                                              Z  Y  W  X        Q         salt                                                                              mp °C.                              __________________________________________________________________________     2 CF.sub.3                                                                         Cl CN                                                                                ##STR13##                                                                              ##STR14##                                                                              HCl 141-144                                     3 CF.sub.3                                                                         Cl CN                                                                                ##STR15##                                                                              ##STR16##                                                                              HCl 210-213                                     4 CF.sub.3                                                                         Cl CN                                                                                ##STR17##                                                                              ##STR18##                                                                              HCl 189-191                                     5 CF.sub.3                                                                         Cl CN                                                                                ##STR19##                                                                              ##STR20##                                                                              HCl 227- 229                                    6 CF.sub.3                                                                         Br CN                                                                                ##STR21##                                                                              ##STR22##                                                                              free base                                                                         135-137                                     7 CF.sub.3                                                                         Br CN                                                                                ##STR23##                                                                              ##STR24##                                                                              HBr 228-230                                     8 CF.sub.3                                                                         Br CN                                                                                ##STR25##                                                                              ##STR26##                                                                              HBr >225                                        9 CF.sub.3                                                                         Br CN                                                                                ##STR27##                                                                              ##STR28##                                                                              HBr 215-218 (dec)                              10 CF.sub.3                                                                         Br CN                                                                                ##STR29##                                                                              ##STR30##                                                                              HBr 224-227                                    11 CF.sub. 3                                                                        Br CN                                                                                ##STR31##                                                                              ##STR32##                                                                              HBr 232-234 (dec)                              12 CF.sub.3                                                                         Br CN                                                                                ##STR33##                                                                              ##STR34##                                                                              HBr 128-130                                    13 Br Br CN Br                                                                                      ##STR35##                                                                              HBr 215 (dec)                                  14 Br Br CN Br                                                                                      ##STR36##                                                                              HCl 216                                        15 Cl Cl CN                                                                                ##STR37##                                                                              ##STR38##                                                                              HCl 180-184                                    16 CF.sub.3                                                                         Br CN                                                                                ##STR39##                                                                              ##STR40##                                                                              free base                                                                         124.5-125.5                                17 CF.sub.3                                                                         CF.sub. 3                                                                        Br                                                                                ##STR41##                                                                              ##STR42##                                                                              HCl 225-228 (dec)                              18 CF.sub.3                                                                         CF.sub.3                                                                         Br                                                                                ##STR43##                                                                              ##STR44##                                                                              HCl 221 (dec)                                  19 Cl CN Cl                                                                                ##STR45##                                                                              ##STR46##                                                                              HCl 194-197                                    20 Br Br CN Br                                                                                      ##STR47##                                                                              HCl 225 (dec)                                  __________________________________________________________________________     Ex. No. designates Example Number                                        

EXAMPLE 21 Preparation of[3-Chloro-5-(p-chlorophenyl)-4-cyano-2-(trifluoromethyl)pyrrole-1-yl]dimethyldithiocarbamicacid, methyl ester ##STR48##

A mixture of4-chloro-1-(chloromethyl)-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile(0.7 g, 0.002 mol) and dimethyldithiocarbamic acid, sodium salt (0.57 g,0.004 mol) in dimethyl formamide is heated at 50°-55° for 30 minutes,cooled to room temperature and poured into water. The resultant mixtureis extracted with ethyl acetate. The combined extracts are washed with asaturated sodium chloride solution, dried (MGSO₄) and concentrated invacuo to give an orange oil residue. The residue is mixed with hothexane, cooled and filtered to give an orange solid filtercake.Recrystallization of the solid from isopropanol gives the title productas a tan crystaline solid, 0.7 g (80% yield), mp 129°-131° C.

EXAMPLES 22-43 Preparation of [(substitutedpyrrole-1-yl)dithiocarbamate, thiocarbamate and thiophosphate methylesters and thioalkyl derivatives

Using the procedure described in Example 21 and employing theappropriately substituted 1-halo

                                      TABLE II                                    __________________________________________________________________________     ##STR49##                                                                    Ex.                                                                           No.                                                                              Z  Y  W  X          Q         mp °C.                                __________________________________________________________________________    22 CF.sub.3                                                                         Cl CN                                                                                ##STR50##                                                                                ##STR51##                                                                              94-95                                        23 CF.sub.3                                                                         Cl CN                                                                                ##STR52##                                                                                ##STR53##                                                                              (oil)                                        24 CF.sub.3                                                                         Br CN                                                                                ##STR54##                                                                                ##STR55##                                                                              125-128                                      25 CF.sub.3                                                                         Br CN                                                                                ##STR56## CH.sub.3                                               26 CF.sub.3                                                                         Br CN                                                                                ##STR57##                                                                                ##STR58##                                                                              101-103                                      27 CF.sub.3                                                                         Br CN                                                                                ##STR59##                                                                                ##STR60##                                                                              108-110                                      28 Cl Cl CN                                                                                ##STR61##                                                                                ##STR62##                                                                              82-85                                        29 CF.sub.3                                                                         Br CN                                                                                ##STR63##                                                                                ##STR64##                                                                              85-86                                        30 CF.sub.3                                                                         Br CN                                                                                ##STR65##                                                                                ##STR66##                                                                                120-121.5                                  31 Br Br CN Br                                                                                        ##STR67##                                                                              170-172                                      32 Cl Cl CN                                                                                ##STR68##                                                                                ##STR69##                                                                              194-197                                      33 CF.sub.3                                                                         CF.sub.3                                                                         Br                                                                                ##STR70##                                                                                ##STR71##                                                                              128-129                                      34 Br Br CN Br                                                                                        ##STR72##                                                                              135-137                                      35 CF.sub.3                                                                         CF.sub.3                                                                         Br                                                                                ##STR73##                                                                                ##STR74##                                                                              (oil)                                        36 Cl CN Cl                                                                                ##STR75##                                                                                ##STR76##                                                                              120-123                                      37 Cl CN Cl                                                                                ##STR77##                                                                                ##STR78##                                                                              100-105                                      38 Br Br CN Br         CN        168-170                                      39 Br Br CN                                                                                ##STR79##                                                                                ##STR80##                                                                              50-53                                        40 Br Br CN Br                                                                                        ##STR81##                                                                                106-110.5                                  41 CF.sub.3                                                                         Br CN                                                                                ##STR82##                                                                                ##STR83##                                                                              106-110                                      42 CF.sub.3                                                                         Br CN                                                                                ##STR84## CN        95-97                                        43 Br Br CN CH.sub.3 S CH.sub.3  110-111                                      __________________________________________________________________________     Ex. No. designates Example Number   methylpyrrole and the sodium salt of      the desired dithiocarbamate, thiocarbamate, thiophosphate or mercaptate     reagent the following compounds shown in Table II are obtained.

                                      TABLE II                                    __________________________________________________________________________     ##STR85##                                                                    Ex.                                                                           No.                                                                              Z  Y  W  X          Q         mp °C.                                __________________________________________________________________________    22 CF.sub.3                                                                         Cl CN                                                                                ##STR86##                                                                                ##STR87##                                                                              94-95                                        23 CF.sub.3                                                                         Cl CN                                                                                ##STR88##                                                                                ##STR89##                                                                              (oil)                                        24 CF.sub.3                                                                         Br CN                                                                                ##STR90##                                                                                ##STR91##                                                                              125-128                                      25 CF.sub.3                                                                         Br CN                                                                                ##STR92## CH.sub.3                                               26 CF.sub.3                                                                         Br CN                                                                                ##STR93##                                                                                ##STR94##                                                                              101-103                                      27 CF.sub.3                                                                         Br CN                                                                                ##STR95##                                                                                ##STR96##                                                                              108-110                                      28 Cl Cl CN                                                                                ##STR97##                                                                                ##STR98##                                                                              82-85                                        29 CF.sub.3                                                                         Br CN                                                                                ##STR99##                                                                                ##STR100##                                                                             85-86                                        30 CF.sub.3                                                                         Br CN                                                                                ##STR101##                                                                               ##STR102##                                                                               120-121.5                                  31 Br Br CN Br                                                                                        ##STR103##                                                                             170-172                                      32 Cl Cl CN                                                                                ##STR104##                                                                               ##STR105##                                                                             194-197                                      33 CF.sub.3                                                                         CF.sub.3                                                                         Br                                                                                ##STR106##                                                                               ##STR107##                                                                             128-129                                      34 Br Br CN Br                                                                                        ##STR108##                                                                             135-137                                      35 CF.sub.3                                                                         CF.sub.3                                                                         Br                                                                                ##STR109##                                                                               ##STR110##                                                                             (oil)                                        36 Cl CN Cl                                                                                ##STR111##                                                                               ##STR112##                                                                             120-123                                      37 Cl CN Cl                                                                                ##STR113##                                                                               ##STR114##                                                                             100-105                                      38 Br Br CN Br         CN        168-170                                      39 Br Br CN                                                                                ##STR115##                                                                               ##STR116##                                                                             50-53                                        40 Br Br CN Br                                                                                        ##STR117##                                                                               106-110.5                                  41 CF.sub.3                                                                         Br CN                                                                                ##STR118##                                                                               ##STR119##                                                                             106-110                                      42 CF.sub.3                                                                         Br CN                                                                                ##STR120##                                                                              CN        95-97                                        43 Br Br CN CH.sub.3 S CH.sub.3  110-111                                      __________________________________________________________________________     Ex. No. designates Example Number                                        

EXAMPLE 44 Preparation of4,5-dibromo-1[(methylthio)methyl]-2-(α,α,α-trifluoro-p-tolyl)pyrrole-3-carbonitrile##STR121##

A solution of4,5-dibromo-2-(α,α,α-trifluorop-tolyl)pyrrole-3-carbonitrile (0.56 g,1.42 mmol) in dry tetrahydrofuran, under nitrogen, is treatedportion-wise with potassium t-butoxide (0.21 g, 1.81 mmol), stirred at25° C. for 3/4 hour, treated dropwise with chloromethyl methyl thioether(0.18 g, 1.81 mmol), stirred at room temperature for 16 hours, heated at49°-60° C. until reaction is complete by thin layer chromatography. Thereaction mixture is diluted with water and ether. The phases areseparated and the organic layer is dried over MGSO₄ and concentrated invacuo to give a black oil residue. The residue is flash chromatographed(silica/100:100:1 ether:petroleum ether:ethyl acetate) to give the titleproduct as a red solid, mp 140°-145° C., identified by H¹ NMR and massspectral analyses.

EXAMPLE 45 Preparation of4.5-dibromo-1[(phenylthio)methyl]-2-(α,α,α-trifluoro-p-tolyl)pyrrole-3-carbonitrile##STR122##

Following the procedure described in Example 44, above, and substitutingchloromethyl phenyl thioether as the alkylating reagent, the titleproduct is obtained as a red oil, bp >200° C./0.7 mmHg, identified by H¹NMR, C¹³ NMR and mass spectral analyses.

EXAMPLE 46 Preparation of4-bromo-2-(p-chlorophenyl)-1-[(phenylsulfonyl)methyl]-5-trifluoromethyl)pyrrole-3-carbonitrile##STR123##

A stirred solution of4-bromo-1-(bromomethyl)-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile(0.65 g, 1.5 mmol) in dry dimethyl formamide is treated with sodiumbenzylsulfonate (0.485 g, 3.0 mmol), heated at 700° C. for 3 hours,cooled to room temperature and diluted with a mixture of water and ethylacetate. The organic phase is separated, dried over MGSO₄ andconcentrated in vacuo to give a yellow oil residue. Columnchromatography (silica gel/4:1 hexanes:ethyl acetate) gives the titleproduct as a white solid, mp 165°-166.50° C., identified by H¹ NMR andmass spectral analyses.

EXAMPLE 47 Insecticidal and acaricidal evaluations of test compounds

Test solutions are prepared by dissolving the test compound in a 35%acetone in water mixture to give a concentration of 10,000 ppm.Subsequent dilutions are made with water as needed.

Heliothis virescens, egg, tobacco budworm

A young cotton leaf about 6-7 cm in length is dipped in an agitated testsuspension for about 3 seconds. Eggs are collected on a cheesecloth andthe cloth is cut into 10-20 mm squares, each containing approximately50-100 eggs which are 6-30 hours old. The egg-containing cheeseclothsquare is similarly dipped in a test suspention and placed on a treatedcotton leaf. The combination is dried in a hood and then placed in an 8ounce Dixie® cup #2168-ST (240 ml volume, 6 cm tall, 9.5 cm topdiameter, 8.0 cm bottom diameter) into which a 5 cm length of dampdental wick has been placed. The cup is covered with a clear plastic lidand held for 3 days, after which mortality counts are made.

Heliothis virescens, 3rd instar tobacco budworm

Cotton cotyledons are dipped in the test solution and allowed to dry ina hood. When dry, each is cut into quarters and ten sections are placedindividually in 30 mL plastic medicine cups containing a 5-7 mm longpiece of damp dental wick. One 3rd instar caterpillar is added to eachcup and the cup is sealed with MYLAR® film. Treatments are maintainedfor 3 days before a mortality count and observation of reduction infeeding damage are made.

Spodoptera eraeridania, 3rd instar larvae, southern armyworm

A Sieva limabean leaf expanded to 7-8 cm in length is dipped in the testsolution with agitation for 3 seconds and allowed to dry in a hood. Theleaf is then placed in a 100×10 mm petri dish containing a dampfilterpaper on the bottom and ten 3rd instar caterpillars. At 3 and 5days, observations are made of mortality, reduced feeding, or anyinterference with normal molting.

Spodoptera eridania, 3rd instar larvae, southern armyworm, 7-dayresidual

The limabean leaves treated in the above test are maintained under highintensity lamps in the greenhouse for 7 days. These lamps duplicate theeffects of a bright sunny day in June in New Jersey and are kept on for14 hour day length. After 7 days, the foliage is sampled and assayed asin the above-said test.

Spodoptera eridania, systemic uptake, 3rd instar larvae. southernarmyworm

An emulsion containing 0.1 gm of the test compound, 0.2 gm of EmulphorEL-620® emulsifier, 10 mL of acetone and 90 mL of water is prepared anddiluted 10-fold with water to give a 100 ppm emulsion. Subsequent10-fold dilutions are made with water as needed. Sieva limabean plants,with the primary leaves expanded to a length of 7-8 cm, are cut off atleast 3 cm above the soil level to avoid contamination with soilbacteria which will cause decay of the stem during the test. The cutstem is placed in the test emulsion and wrapped with a bit of cotton tohold the stem off the bottom of the bottle and to limit evaporation. Thetreated stem is thus maintained for 3 days at 270° C. to allow the testcompound to be taken up into the plant. Following this, one leaf isremoved from the plant and placed in a 100×10 mm petri dish with 10southern armyworms as described above. Mortality counts and observationsof feeding damage are made 3 and 5 days later.

Diabrotic undecimpunctata howardi, 3rd instar southern corn rootworm

One cc of fine talc is placed in a 30 mL wide-mouth screw-top glass jar.One mL of the appropriate acetone test solution is pipetted onto thetalc so as to provide 1.25 and 0.25 mg of active ingredient per jar. Thejars are set under a gentle air flow until the acetone is evaporated.The dried talc is loosened, I cc of millet seed is added to serve asfood for the insects and 25 mL of moist soil is added to each jar. Thejar is capped and the contents thoroughly mixed on a Vortex Mixer.Following this, ten 3rd instar rootworms are added to each jar and thejars are loosely capped to allow air exchange for the larvae. Thetreatments are held for 6 days when mortality counts are made. Missinglarvae are presumed dead, since they decompose rapidly and can not befound. The concentrations used in this test correspond approximately to50 and 10 kg/ha, respectively.

Tetranychus urticae (OP-resistant strain), 2-spotted spider mite

Sieva limabean plants with primary leaves expanded to 7-8 cm areselected and cut back to one plant per pot. A small piece is cut from aninfested leaf taken from the main colony and placed on each leaf of thetest plants. This is done about 2 hours before treatment to allow themites to move over to the test plant and to lay eggs. The size of thecut, infested leaf is varied to obtain about 100 mites per leaf. At thetime of test treatment, the piece of leaf used to transfer the mites isremoved and discarded. The newly mite-infested plants are dipped in thetest solution for 3 seconds with agitation and set in the hood to dry.After 2 days one leaf is removed and mortality counts are made. After 5days, another leaf is removed and observations are made of mortality ofthe eggs and/or newly emerged nymphs.

Aphis fabae, mixed instar, bean aphid

Pots containing single nasturtium plants (Tropaeolum sp.) about 5 cmtall are infested with about 100-200 aphids one day prior to treatment.Each pot is sprayed with the test solution for 2 revolutions of a 4 rpmturntable in a hood, using a #154 DeVilbiss atomizer. The spray tip isheld about 15 cm from the plant and the spray directed so as to givecomplete coverage of the plants and the aphids. The sprayed pots are seton their sides on white enamel trays and mortality estimates are madeafter 2 days.

Empoasca abrupta, adult, western potato leafhopper

A Sieva limabean leaf about 5 cm long is dipped in the test solution for3 seconds with agitation and placed in a hood to dry. The treated leafis place in a 100×10 mm petri dish containing a moist filter paper andabout 10 adult leafhoppers are added. After 2 days, mortality counts aremade.

Empoasca abrupta, adult, western potato leafhopper Systemic Uptake

An emulsion containing 0.1 gm of the test material, 0.2 gm of EmulphorEL-620® emulsifier, 10 mL of acetone and 90 mL of water is prepared anddiluted 10-fold with water to give a 100 ppm emulsion. Subsequent10-fold dilutions are made with water as needed. Sieva limabean plants,with the primary leaves expanded to a length of 7-8 cm, are cut off atleast 3 cm above the soil level to avoid contamination with soilbacteria which will cause decay of the stem during the test. The cutstem is placed in the test emulsion and wrapped with a bit of cotton tohold the stem off the bottom of the bottle and to limit evaporation. Thetreated stem is maintained for 3 days at 270° C. to allow the testcompound to be taken up into the plant. Following this, one leaf isremoved from the plant and placed in a 100×10 mm petri dish containing amoist filter paper and about 10 adult leafhoppers as described above.Mortality counts are made after 2 days.

All of the above tests are rated according to the rating scale shownbelow.

    ______________________________________                                        Rating Scale:                                                                 ______________________________________                                        0 = no effect       5 = 56-65% kill                                           1 = 10-25% kill     6 = 66-75% kill                                           2 = 26-35% kill     7 = 76-85% kill                                           3 = 36-45% kill     8 = 86-99% kill                                           4 = 46-55% kill     9 = 100% kill                                             ______________________________________                                    

The data obtained are shown in Tables III and IV wherein the testcompounds are identified by Example Number.

                                      TABLE III                                   __________________________________________________________________________    Insecticidal And Acaricidal Evaluation Of Test Compounds                                                                             SOUTHERN               TOBACCO BUDWORM            ARMYWORM                    CORN                                      3rd                                 ROOTWORM               Compound                                                                            Egg (ppm)    Instar (ppm)                                                                          Day 3 (ppm)                                                                             Day 5 (ppm)                                                                             Stem Sys                                                                              (ppm)                  (Ex. No.)                                                                           1000 300 100 1000                                                                             100                                                                              10                                                                              1000                                                                             100                                                                              10                                                                              R 1000                                                                             100                                                                              10                                                                              R 1000    50 10 1                __________________________________________________________________________    44    0    --  --  9  0  0 9  9  0 0 9  9  0 2 0       3  0  --               45    0    --  --  0  0  --                                                                              8  0  --                                                                              0 8  0  --                                                                              0 0       0  -- --                2    0    --  0   9  9  9 9  9  9 9 9  9  9 9 0       8  0  0                 3    5    --  0   9  9  8 9  9  8 --                                                                              9  9  9 --                                                                              0       9  0  0                22    0    --  --  9  9  3 9  9  9 --                                                                              9  9  9 --                                                                              0       9  8  3                23    0    --  --  9  9  5 9  9  9 --                                                                              9  9  9 --                                                                              --      9  6  0                 4    9    --  9   9  9  9 9  9  9 9 9  9  9 9 0       0  -- --               25    0    --  --  9  9  8 9  9  0 9 9  9  0 9 0       0  0  --                5    0    --  --  9  9  0 9  9  4 9 9  9  4 9 8       0  -- --               21    0    --  0   9  9  9 9  9  9 9 9  9  9 9 0       9  0  0                24    0    --  --  9  9  0 9  9  9 9 9  9  9 9 0       9  0  0                46    0    --  --  9  4  --                                                                              9  0  0 4 9  0  0 9 0       8  0  0                 6    0    --  --  9  8  0 9  9  0 9 9  9  5 9 0       9  5  0                 7    9    8   0   9  9  5 9  9  9 9 9  9  9 9 0       9  0  0                 8    0    --  0   9  9  3 9  9  0 9 9  9  6 9 9       0  -- --                9    0    --  --  0  0  --                                                                              6  0  --                                                                              9 7  0  --                                                                              9 0       0  -- --               10    0    --  0   9  8  0 9  9  0 9 9  9  0 9 0       0  -- --               11    5    --  3   9  9  6 9  9  9 9 9  9  9 9 9       0  -- --               12    0    --  --  9  9  8 9  9  9 9 9  9  9 9 0       8  9  0                26    0    --  --  9  9  9 9  9  9 9 9  9  9 9 0       9  4  0                27    0    --  --  9  7  0 9  9  0 9 9  9  0 9 0       9  7  6                 1    0    --  0   9  9  4 9  9  9 9 9  9  9 9 0       0  -- --               28    0    --  0   9  3  0 9  9  6 9 9  9  6 9 0       0  -- --               29    4    --  0   9  9  4 9  9  9 9 9  9  9 9 0       9  -- --               30    0    --  0   9  9  4 9  9  9 9 9  9  9 9 0       9  -- --               13    0    --  --  0  -- --                                                                              9  0  --                                                                              0 9  3  --                                                                              7 7       0  -- --               31    0    --  --  6  -- --                                                                              9  9  0 9 9  9  0 9 0       0  -- --               14    0    --  --  8  0  --                                                                              9  9  0 0 9  9  0 5 0       0  -- --               15    0    --  0   9  6  0 9  9  9 9 9  9  9 9 0       0  -- --               32    0    --  --  0  0  --                                                                              9  3  0 0 9  3  0 0 0       0  -- --               16    0    --  0   9  9  9 9  9  9 9 9  9  9 9 4       9  -- --               17    0    --  --  9  8  8 9  9  9 9 9  9  9 9 0       7  -- --               18    0    --  --  9  9  0 9  9  0 9 9  9  0 9 0       0  -- --               33    0    --  --  9  9  7 9  9  9 9 9  9  9 9 0       -- -- --               43    0    --  --  0  -- --                                                                              9  0  0 * 9  0  0 * 0       0  -- --               34    8    --  --  9  0  --                                                                              9  9  5 * 9  9  5 * 0       0  -- --               35    0    --  --  9  9  8 9  9  9 9 9  9  9 9 0       0  -- --               36    0    --  --  9  9  0 9  9  8 9 9  9  8 9 0       0  -- --               19    0    --  --  9  9  0 9  9  0 9 9  9  0 9 0       0  -- --               37    0    --  --  9  9  0 9  9  9 9 9  9  9 9 0       0  -- --               38    --   --  --  -- -- --                                                                              9  -- --                                                                              9 -- -- --                                                                              0 --      --                     20    0    0   0   9  0  0 9  9  0 6 9  9  0 * --      0  -- --               40    0    --  --  0  0  --                                                                              9  0  0 0 9  0  0 * 0       0  -- --               __________________________________________________________________________     R designates Residual                                                         Stem Sys designates Stem Systemic                                        

                                      TABLE IV                                    __________________________________________________________________________    Insecticidal And Acaricidal Evaluation of Test Compounds                      OP-RESISTANT MITES                 LEAFHOPPER                                       Adult   Egg     Nymph   APHIDS                                                                             Contact                                                                            Systemic                              Compound                                                                            (ppm)   (ppm)   (ppm)   (ppm)                                                                              (ppm)                                                                              (ppm)                                 (Ex. No.)                                                                           300                                                                              100                                                                              10                                                                              300                                                                              100                                                                              10                                                                              300                                                                              100                                                                              10                                                                              100  100                                                                              10                                                                              100                                   __________________________________________________________________________    44    9  7  0 0  7  0 8  0  5 0    7  0 0                                      2    9  9  8 0  9  0 9  -- 7 0    9  8 0                                     3     4  9  8 4  9  1 9  -- 0 0    9  9 0                                     22    9  9  9 0  9  9 9  -- --                                                                              7    9  9 0                                     23    9  9  9 0  9  9 9  -- --                                                                              5    9  9 0                                      4    9  6  0 9  0  0 -- 0  0 0    9  0 0                                     25    7  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    9  0 0                                      5    9  8  0 0  9  0 0  -- 0 0    9  4 8                                     21    9  9  9 0  8  0 9  0  0 0    9  5 0                                     24    0  9  9 9  9  0 -- -- 0 7    9  0 0                                      7    9  9  9 0  9  0 0  9  5 0                                                8    9  9  0 0  8  4 0  8  0 0    8  0 --                                    10    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    7  0 6                                     11    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    9  8 9                                     12    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    9  5 --                                     1    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    9  7 0                                     28    9  9  3 0  9  0 0  -- 3 0    9  0 0                                     29    9  9  9 0  9  9 0  -- --                                                                              0    9  9 0                                     30    9  9  9 0  9  9 0  -- --                                                                              3    9  8 0                                     13    5  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    0  --                                                                              0                                     14    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    0  --                                                                              7                                     15    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    6  0 0                                     16    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              8    9  9 0                                     17    7  0  0 0  7  0 0  0  0 0    5  --                                                                              0                                     18    9  9  0 0  0  0 0  0  0 0    9  4 0                                     33    7  0  0 0  8  0 0  0  0 0    8  0 0                                     34    0  -- --                                                                              0  -- --                                                                              0  -- --                                                                              8    0  --                                                                              0                                     35    9  9  8 0  9  3 0  -- 0 0    9  9 0                                     36    7  0  0 0  0  0 0  0  0 0    6  --                                                                              0                                     19    5  -- --                                                                              0  -- --                                                                              0  -- --                                                                              0    9  0 0                                     37    7  9  0 0  9  2 0  -- 4 0    6  --                                                                              0                                     __________________________________________________________________________

We claim:
 1. A molluscicidal bait composition which comprises an ediblenutritive substance, a carbohydrate source and a molluscicidallyeffective amount of a compound having the structure ##STR124## wherein Wis CN or NO₂ ; X is halogen or phenyl optionally substituted with one tothree C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkylsulfinyl, C₁ -C₃ alkylsulfonyl, halogen, CN, NO₂, CF₃, R₄ CF₂ B, R₅CO or NR₆ R₇ groups;Y is CF₃, halogen or phenyl optionally substitutedwith one to three C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkylsulfinyl, C₁ -C₃ alkylsulfonyl, halogen, CN, NO₂, CF₃, R₄ CF₂ B, R₅CO or NR₆ R₇ groups; Z is halogen or CF₃ ; R₁ is hydrogen, C₁ -C₆ alkyl,C₃ -C₆ cycloalkyl; R₂ and R₃ are each independently hydrogen, C₁ -C₆alkyl or C₃ -C₆ cycloalkyl; R₄ is hydrogen, fluorine, CHF₂, CHFCl or CF₃; R₅ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₆ R₇ ; R₆ is hydrogen or C₁ -C₃alkyl; R₇ is hydrogen, C₁ -C₃ alkyl or R₈ CO; R₈ is hydrogen or C₁ -C₃alkyl; B is S(O)_(q) or O; m, n, p and q are each independently aninteger of 0, 1 or 2 with the proviso that the sum (p+m) must be greaterthan 0; ##STR125## CN, C₁ -C₆ alkyl optionally substituted with one ormore phenyl, CN or halogen groups or phenyl optionally substituted withone to three C₁ -C₃ alkyl, C₁ -C₃ alkoxy, halogen, CN, NO₂, CF₃ or NR₂₀R₂₁ groups; A is O or S; R₉ is C₁ -C₆ alkyl or phenyl; R₁₀ is C₁ -C₆alkyl; R₁₁ and R₁₂ are each independently hydrogen, C₁ -C₆ alkyl or maybe taken together with the atom to which they are attached to form a 5-to 7-membered ring; R₁₃ is C₁ -C₄ alkyl; R₁₄ is C₁ -C₄ alkyl or may betaken together with either R₁₅ or R₁₇ and the atoms to which they areattached to form a 5- to 7-membered ring optionally substituted with oneor two C₁ -C₃ alkyl groups; R₁₅ and R₁₆ are each independently hydrogenor C₁ -C₄ alkyl; R₁₇ is C₁ -C₄ alkyl or when taken together with R₁₄ andthe atoms to which they are attached may form a 5- to 7-membered ringoptionally substituted with one or two C₁ -C₃ alkyl groups; R₁₈ and R₁₉are each independently hydrogen or C₁ -C₃ alkyl or when taken togethermay form a ring wherein R₁₈ R₁₉ is represented by --CH═CH--CH═CH--; R₂₀and R₂₁ are each independently hydrogen or C₁ -C₃ alkyl and the acidaddition salts thereof.
 2. The molluscicidal bait composition accordingto claim 1 having the structure ##STR126##
 3. The molluscicidal baitcomposition according to claim 1 wherein W is CN; X is halogen or phenyloptionally substituted with one to three halogen, CN or CF₃ groups; Yand Z are each independently halogen or CF₃ ; n and m are O; and p is 1.4. The molluscicidal bait composition according to claim 1 wherein##STR127##
 5. The molluscicidal bait composition according to claim 2wherein W is CN; X is halogen or phenyl optionally substituted with oneto three halogen, CN or CF₃ groups; Y and Z are each independentlyhalogen or CF₃ ; and n is O.
 6. The molluscicidal bait compositionaccording to claim 5 wherein ##STR128##
 7. The molluscicidal baitcomposition according to claim 6 wherein R₁ is hydrogen.
 8. Themolluscicidal bait composition according to claim 7 wherein R₁₀ is C₁-C₆ alkyl, R₁₄, R₁₅ and R₁₆ are each independently hydrogen, C₁ -C₄alkyl or R₁₄ and R₁₅ may be taken together with the atoms to which theyare attached to form a 5- or 6-membered ring and R₁₈ and R₁₉ are eachindependently hydrogen or C₁ -C₃ alkyl.
 9. The molluscicidal baitcomposition according to claim 1 wherein the molluscicidally effectiveamount of the compound of formula I comprises about 3% to 20% by weight.10. The molluscicidal bait composition according to claim 9 comprising,on a weight to weight basis, about 5% to 10% of the compound of formulaI, about 40% to 50% of a solid edible substance, about 5% to 10% of acarbohydrate source and about 30% to 50% of a consummable liquid. 11.The molluscicidal bait composition according to claim 10 wherein saidcarboyhdrate source is selected from the group consisting of sugar,molasses and corn syrup.
 12. The molluscicidal bait compositionaccording to claim 10 wherein said consummable liquid comprises water.